Process for sulphating olefines



July 10, 1934. R. F. LE BARON PRQGESS FOR SULPHATING OLEFINES Filed Apfil 4, 19:50

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- v awwewto'c 93x a t tow f W 023 WW Patented July 10, 1934 PATENT OFFICE PROCESS FOR SULPHATING OLEFINES Robert F. Le Baron, New York, N. Y., assignor, by mesne assignments, to Standard Alcohol Company, Wilmington, Del., a corporation of Delaware Application April 4, 1930, Serial No. 441,624

1 Claim.

My process and apparatus there-for are characterized by a relatively large throughput per unit of investment, by the fact that accurate and complete control of the reaction may be easily maintained thereby, by a'relatively enhanced reaction eificiency, and by the further fact that the fire and explosion hazard due to the inflammable character of the material treated is reduced to an absolute minimum. While my invention is generically applicable to the sulphation of olefines either separately or in admixture with other hydrocarbons, it is of particular advantage in application to the normally gaseous olefines and to those mixtures of hydrocarbons, containing olefines, produced by cracking petroleum oil. Other advantages of the process and apparatus will be .apparent from the following description read in conjunction with the drawing which is a diagrammatic elevation with parts in section of a preferred form of apparatus in which my invention may be carried into effect.

The invention will be illustrated in application to a mixture of hydrocarbons, containing olefines, produced by vapor phase cracking of petroleum oil, carried out, for example, at temperatures between 1050 and 1150 F. The invention is susceptible of application as previously stated either to the olefines separately or to any mixture of hydrocarbons containing olefines. The mixtures of hydrocarbons consisting predominantly of olefines produced by the extensive cracking of petroleum oil carried out, for example, under pressures in excess of 400 pounds to the square inch or in vapor phase at any pressure, present difficulties to successful sulphation, and inasmuch as such mixtures may be successfully handled by my process and apparatus, the same are selected as appropriate material for the following illustrative specific example.

When cracking petroleum oil to produce gasoline, a practically unbroken series of hydrocarbons is obtained extending from hydrocarbons corresponding to the oil cracked through the kerosene, gasoline and gas range, up to and including methane. The composition of such materials depends in large measure upon the cracking conditions; for example, where the cracking is relatively mild, parafiins predominate; and where cracking is relatively extensive, olefines predominate. In either event, the character of the material is extremely complicated containing saturated hydrocarbons, mono olefines of both secondary and tertiary types together with di and higher olefines. Cycle stock, kerosene and gasoline are ordinarily separated from the products pipe 6.

ceeding 100 pounds per square inch are ordinarily of cracking, leaving a residue which is normally gaseous and which consists substantially of hydrocarbons of not exceeding 4 carbon atoms to the molecule together with hydrogen. Such a residue may be supplied to the apparatus through in column 5 with the resultant production of a;

bottoms. containing hydrocarbons of 4 carbon atoms to the molecule which may be withdrawn through pipe 10, controlled by valve 11, and transferred by pump 12 through pipe 13, controlled by valve 14 to storage tank 15. Column 5 is preferably operated under moderate pressure so that the hydrocarbons of 4 carbon atoms may be re-' fluXed by passing ordinary cooling water through For this purpose, pressures of not exsufiicient. The overhead which is substantially free from hydrocarbons of 4 carbon atoms to the molecule passes off through pipe 20, controlled by valve 21, and is compressed in 22 to be delivered through pipe 23, controlled by valve 24, to column 30.

Column carries cooling coil 31 adjacent the upper part thereof and heater coil 32 adjacent the lower part thereof. It is equipped with liquid vapor countercurrent contacting devices similar to those described for column 5. Rectification takes place in column 30 with the resultant production of a bottoms consisting predominantly of hydrocarbons of 3 carbon atoms to the molecule which is withdrawn through pipe 34, controlled by valve 35 and passed by means of pump 36 and pipe 37, controlled by valve 38, to storage tank 39. Column 30 is preferably operated under pressure in excess of atmospheric, inasmuch as this permits the use of ordinary cooling water in coil 31 for reflux purposes. Pressures of not exceeding 500 pounds to the square inch will be found suitable for this purpose. The overhead which is substantially free from hydrocarbons of 3 carbon atoms to the molecule, passes off through pipe 40, controlled by valve 41 to compressor 42 by which it is compressed and introduced through pipe 43; controlled by valve 44, to rectifying column 50.

Column is equipped with cooling coil'51 adjacent the lower part thereof and liquidvapor counter-current contacting devices similar to those previously described in connection with column 5. Column must be'operated at pressures considerably in excess of atmospheric, and coil 51 must be provided with a refrigerating medium inasmuch as the temperature of the bottoms withdrawn through pipe 53 controlled by valve 54 must be below the critical temperature of ethylene, and the reflux supplied by the operation of coil 51 must be relatively cooler. The remanent gas consisting of methane and hydrogen passes off through pipe 60, controlled by valve 61. The bottoms are transferred by pump. 55 through pipe 56, controlled by valve 5'7, to storage tank 58. While I have described three rectifying columns in series, it will be understood that either a greater. or lesser degree of rectification may be resorted to.

Where the remanent gas delivered through pipe 1 is the product of vapor phase cracking, the hydrocarbon material in tank 15 will contain both secondary and tertiary olefines of 4 carbon atoms to the molecule, together with di and possibly higher olefines. I find it particularly advantageous to separate certain components of this material in a series of steps to minimize the heat evolvedat any particular stage, and to permit the maximum output from the apparatus. In one preferred method of accomplishing this purpose, the hydrocarbon material is treated to selectively separate the major part of the butadiene therefrom. This may be accomplished by passing the material through pipe 62, controlled by. valve 62' into the autoclave 63, in which it is agitated with a suspension .of cuprous chloride in an aqueous medium containing preferably ammonium chloride. Mixing may be effected in 63 by rotation of propeller 64' with the consequent formation of a compound of cuprous chloride and Y butadiene which is insoluble in the remainder of the hydrocarbon material. At the conclusion of the reaction, the materials in 63 may be settied and the supernatant hydrocarbon material may be withdrawn through side outlets 64 and transferred through pipe 65 to. storage tank 66. The reaction between cuprouschloride and butadiene in autoclave 63 is preferably carried out at temperatures below 10 C. A number of alternative methods for the removal of the butadiene may be employed, and this subject together with the regeneration of the cuprous chloride for further use is more completely described in co-pending application of Benjamin T. Brooks, Serial No. 433,426, filed, March 5, 1930.

The hydrocarbon material from tank 66 may now be transferred by pump 6'7 through pipe 68, controlled by valve 69, to pump 70, which is preferably a proportioning pump having a common steam end '71, operating liquid ends '72 and '73. Simultaneously, a continuous stream of aqueous sulphuric acid is introduced to liquid end '73, through pipe '74, controlled by valve '75. The

operations in this stage are directed primarily to' the selective removal of any tertiary olefines present. For this purpose, an aqueous sulphuric acid of from 55 to 65%, H1804 content, may be employed; although I prefer a concentration of from 55 to 60%. The amount of sulphuric acid will, oi! course, be suitably proportioned to remove the major .part and preferably substantially all of the'tert'iary olefines present in the hydrocarbon material. The hydrocarbon material from liquid end '72 may pass through-pipe 80,

controlled by valve 81 into pipe 82, while the aqueous sulphuric acid from liquid end '73 passes through pipe 90, controlled by valve 91 into pipe 82 in which the two streams combine. In my preferred procedure, however, the hydrocarbon material from pipe is passed by manipulation of valves 81 and 83 into the precooler 84 and is then discharged through pipe 85, controlled by valve 86, into the pipe 82. The aqueous sulphuric acid may be simultaneously passed by manipulation of valves 91- and 92 into precooler 93 from which it flows through pipe 94, controlled by valve 95, into the pipe 82. From pipe 82 the combined streams may be passed by manipulation of valve 100 through the tubular coil 101 in which mixing takes place. Any type of mixer operating to mix a continuous stream of material passing therethrough may be alternatively employed, although the coil type will be found satisfactory. The coil 101 may be surrounded with a suitable liquid medium to hold the temperature of the materials therein within a predetermined range, and the coil should be of sufficient length to permit the materials to remain therein until the reaction is complete. A period of not exceeding one half hour being amply sufficient for this purpose. The hydrocarbon material is in liquid phase throughout, and the system is therefore operated under pressures atleast equal to the vapor pressures of the reacting components in liquid phase.

In my preferred procedure, the combined streams from pipe 82 are passed by manipulating loid mill type, in which the liquid is passed through a relatively narrow slot between two metal sur-, faces at least one of which is in rapid movement, thereby operating to homogenize the hydrocarbon material and aqueous sulphuric acid. This has the effect of accelerating the reaction rate and of permitting the use of relatively weaker sulphuric acid than would otherwise be possible, (other conditions remaining constant) and tends to inhibit polymerization. During this stage of the process, it is highly desirable that temperatures of the reacting materials do not exceed 20 C. and for this reason the degree of precooling applied through the operation of precoolers 84 and/or 93 is so regulated with regard to the heat of reaction as to insure a final temperature of the materials after mixingmot substantially in excess of 20 C.- The mixed materials delivered from either mixer 101 or-mixer 103 pass through pipe 105, controlled by valve 106, and are preferably delivered into the intermediate section of a continuous settler 107 from the lower part of which acid liquor iscontinuously withdrawn through pipe 108, controlled by ,valve 109, while the remanent hydrocarbon material is continuously withdrawn from the upper part of 107, through pipe 110, controlled by valve 111,andsotransferred to storage tank 112.

The acid liquor withdrawn through pipe 108 consists.predominantly of tertiary butyl sulphate and may, for example, be worked up by dilution and distillation for the production of tertiary butyl alcohol.

The final stage of the process is directed to the sulphation of the secondary olefines in the remanent hydrocarbon material. Inasmuch as both diolefines and tertiaries have been preliminarily removed the heat of reaction is not excessive, and relatively large volumes of the material may be expeditiously treated with the evolution of only moderate quantities of heat and consequent relative ease andcontrol. For this purpose, a contin- -valve 102 into the'mixer 103 which is of the colnous stream of the material is withdrawn from tank 112, through pipe 120, controlled by valve 121 and transferred to liquid end 122 of proportioning pump 123. This pump comprises steam end 124 and liquid ends 122 and 125 connected to 124, thereby operating to deliver proportionate quantities of two liquids. Aqueous sulphuric acid is supplied through pipe 127, controlled by valve 128 to liquid end 125. This sulphuric acid may have a concentration of from 65 to 75%, an acid of from 68 to 72% being preferred. Such an acid in quantity sumcient to sulfate the secondary olefines present, together with a slight excess, say 5 or 10 is delivered into pipe 130, controlled by valve 131, passing into pipe 132, while the corresponding stream of hydrocarbon material passes through pipe 133, controlled by valve 134, into the pipe 132.

In my preferred procedure, the streams do not combine immediately in pipe 132, but are first passed by appropriate manipulation of valves 131, 134, 140 and 141 into precoolers 142 and 143, from which the respective streams pass through pipes 142 and 143 into the pipe 132. The combined streams may then pass through pipe 150, con trolled by valve 151 to the coil mixer 152. To complete the reaction, a period of not exceeding one. half hour should be allowed for transit through coil 152,. and this coil may be surrounded with a suitable fluid medium adapted to hold the temperature of the reacting components below a predetermined maximum and preferably between 20 and 25 C. i

In my preferred procedure, the combined streams from pipe 132 are diverted through pipe 160, controlled by valve 161 to mixer 162 which is of the colloid mill type and similar to 103 previously described. The precoolers 142 and 143 are preferably operated to precool the hydrocarbon material and/or the aqueous sulphuric acid to such a degree as to prevent the attainment dur ing mixing of a temperature substantially in excess of 25 C. This temperature is merely a preferred limit and the reaction may be carried out at higher temperatures if desired. After mixing, the materials may be delivered through' pipe 170 and pump 171 to storage tank 172. From 172 the material may be withdrawn continuously or periodically and diverted through pipe 173, con trolled by valve 174 to the distributor 175, by which the material is dispersed into water preliminarily charged to autoclave 176. This is for the purpose of diluting and hydrolyzing the acid liquor. Mixing is effected during this stage by rotating propeller 177, and a cooling medium is preferably introduced through pipes 178 and 179 to jacket 180 for the purpose of holding the temperature below 20 C. The diluted acid liquor may be withdrawn through pipe 181 to be worked up by distillation for secondary butyl alcohol and/ or for conversion into other desired products.

The material in tank 39 consisting of hydrocarbons of 3 carbon atoms to the molecule may contain traces of propane but will consist predominantly of olefines, such as propylene, and may contain propadiene. A continuous stream of this material may be withdrawn through pipe 200, controlled by valve 201 to the liquid end 203 of pump 204 which is preferably a proportioning' pump having a steam end 205 directly connected to liquid ends 203 and 206. A continuous stream of aqueous sulphuric acid is simultaneously introduced through pipe 210, controlled by valve 211 to liquid end 206. The liquid deliveredby 203 may pass through pipe 212, controlled by valve 220 through precoolcr 221, while the sulphuric acid may be simultaneously passed by manipulation of valve 222, through precooler 223. Theprecooled hydrocarbon from 221 is delivered as a continuous stream through pipe 230, controlled by valve 231, into pipe 214, while the precooled sulphuric acid may be simultaneously delivered through pipe 232, controlled by valve 233, into the pipe 214. The combined streams from pipe 214 may be diverted through pipe 240, controlled by valve 241, into the tubular coil 242 in which mixing takes place. The coil 242 may be surrounded by a suitable liquid medium adapted to hold the temperature of the'reacting materials within predetermined limits.

It will, of course, be understood that any alternativemixing device effective to mix a continuous stream of liquid material passing there through may be substituted for coil 242. In my preferred procedure, however, the combined stream from pipe 214 is passed through pipe 250, controlled by valve 251, into the mixer 252 which is of the colloid mill type similar to 103 previously described. Owing to the efiiciency of mixng, I find in each case that a slightly more diluted sulphuric acid can be made to perform work which would require a stronger acid, other conditions remaining the same. This effects an improvement in each case in the yield of sulphated olefine material attributable at least in part to a lesser degree of polymerizaticn together with a saving in the expense of reconcentrating sulphuric acid for use after dilution. The strength of aqueous sulphuric acid adapted to treat propylene in liquid phase I havefound torange between 65 and 75%. My preferred range is from 68 to 72%. Acid of about 70% strength will be found satisfactory for use in this process. When operating under these conditions, there is a measurable though slight heat of reaction, and it may be desirable to precool the hydrocarbon material and/or sulphuric acid in precoolers 221 and 223 to hold the final mixed products below a predetermined maximum temperature. This precooling may, for example, be sufficient to prevent the attainment of a final temperature substantially in excess of 25 C. The mixing is carried out with the hydrocarbon material in liquid phase and for this reason the system is operated under pressures at least equal to the vapor pressure of the reacting components in liquid phase.

The combined mixed streams are discharged through pipe 260, controlled by valve 261, into storage tank 262, from which the material may be carbon material not in solution' may be Withcontinuously or periodically withdrawn through pipe 263, controlled by valve 264, and discharged through distributor 265 into autodrawn through pipe 280, controlled by valve 281, to be worked up for. isopropyl alcohol.

The ethylene fraction in tank 58 may be supplied as a continuous stream of liquid hydrocarbon through pipe300 controlled by valve 301 to the liquid end 302 of proportiohing pump 303, which comprises steam end 304 directly connected to liquid ends 302 and 305. A continuous stream of hydrocarbon material is delivered from 302 through pipe 310, and may be passed by manipulating valve 311 into pipe 312. A continuous stream of aqueous sulphuric acid preferably of from to 90%, H2804 content, for example about is introduced through pipe 315, controlled by valve 316 to liquid end 305, by which itis discharged through pipe 320, controlled by valve 321, to pipe 312.

Alternatively, the acid may be passed by manipulation of valves 32l'and 322 through precooler 323, while the hydrocarbon material may be passed by manipulation of valves 311 and 325 through precooler 326. The material from said precoolers may pass throughpipes 327 and 328, controlled by valves 329 and 330, into the pipe 312. The combined streams may be diverted through pipe 340, controlled by valve 341, to the tubular coil 342 in which mix'ng takes place. While the coil is diagrammatically indicated, it should be of relatively great length so that a period of a few hours is required tocompletely traverse the same. Owingto the relatively low temperatures required which should be below the critical temperature or ethylene, the reaction'takes place rather slowly. The temperatures may be held within the desired limits by surrounding coil 342 with a suitable refrigerating medium. Alternatively, these temperature limits may be main tained by the alternative or simultaneous operation of precoolers 323 and 326. The coil type of mixer 342 is particularly efficacious with the liquid ethylene fraction owing to the extremely high pressures involved ranging between 1000 and 2000 pounds to the square inch. I may a1- ternatively, however, divert the combined stream from pipe 312 through pipe 350, controlled by valve 351, into the mixer 352 which is of the colloid mill type similar to the units 103 and 252 previously described, excepting that it is of especially rugged construction to withstand pressures involved.

The colloid mill type of mixer employed is preferably jacketed so that it may be refrigerated during use to prevent undue rise in temperature, and precoolers 323 and 326 are preferably operated simultaneously. The combined mixed streams consisting of acid liquor, together with any hydrocarbon material not in solution, passes through pipe 360, controlled by valve 361, into reciving tank 362. The unconverted hydrocarbon material may, if desired, be evaporated of! at this stage leaving an acid liquor consisting premominantly of ethylene monosulphate. The acid liquor is passed through pipe 363, controlled by valve 364, and discharges through distributor 365 into autoclave 366. Autoclave 366 will have been preliminarily charged with water for dilution of acid liquor. During thisstage mixing is effected by rotation of propeller 367, and a cooling medium is preferably introduced through pipes 370 and 371-. to jacket 372 to prevent the attainment of temperatures in excess of 20 C.

The diluted acid liquor may be continuously or periodically withdrawn through pipe 380, controlled by valve'381, to be worked up for ethyl alcohol and/or other desired products. I

The foregoing specific description is for purposes of illustration and inasmuch as the process may be carried out with various modifications both of procedure and equipment, it is my intention that the invention be limited only by the appended claim or its equivalents wherein I have endeavored to claim broadly all inherent novelty.

I claim: Process for making alkyl sulphates of a plurality of olefines contained in a hydrocarbon mixture, comprising reacting on the olefines in suc-' ccssive stages with sulphuric acid of progressively increasing strength, in each of said stages the reaction being conducted while the olefine material and acid are continuously flowing in a stream through a mixing zone the temperature of which is controlled to prevent undesirable reactions while permitting the sulphation of the olefine material, continuously withdrawing the resulting product from each stage, and separating the acid reaction product from the unreacted hydrocarbon material. 

